Condensation products of pseudothiohydantoin&#39; protein and process for producing same



Patented Sept. 4, 1945 UNITED STATES PATENT OFFICE CONDENSATION PRODUCTS OF PSEUDO- THIOHYDANTOIN PROTEIN AND PROCESS FOR PRODUCING SAME Oskar Huppert, Newark, N. J.

No Drawing. Application May 24, 1944,

Serial No. 537,190

. 4 Claims.

This application is a continuation-in-part of Serial No. 431,082, new Patent 2,343,012.

This invention relates to the preparation and uses of solutions of condensation-products oi pseudothiohydantoin-zeinand their use with or without a fixing agent in the coating, impregnating and sizing of fibrous materials, textiles, paper, wood, metallic surfaces, further in the manufacture of castings, rubber-like materials, filaments, films.

It is an object of this invention the preparation of stable, non-gelling solutions of condensation-products of pseudothiohydantoin-zein and gelatine with anhydrides of dibasic acids and their reactions-products with a fixing agent, such as formaldehyde, aluminium, chrome salts, tanning agents, whereby under the influence of the anhydrides the globular stage of the prolamine is changed in the more fibrous stage.

A further object is the process of applying these solutions and especially such prepared with aqueous alcohol to fibrous materials such as textiles, paper, wood, metallic surfaces and zein wherein zein stands for the prolamine radical, the prolamine zein, signified as NHz-zein', does react by condensation with the active methylen group in position 5 in the thiazolidon ring in the same manner with phthalic anhydride as N phenyl rhodanine, prepared by F. Kucera (Monatshefte, 35, 137-57, Ch. A. 8.1573) forming 5 phthaliden-3 promaline (zein) pseudothiohydantoin as follows:

o.11.*c=o----s \C=NH 0- 0-N 7 Join A similar reaction takes place with sucoinic, glutaric,maleic, adipic, sebacic anhydride.

To produce filaments, rubber-like materials from globular proteins, prolamines, it is essential to transform the globular stage in molecules of long, rigid elastic fibers, in the more fibrous stage. This transformation is brought about under the influence of phthalic anhydride and the production of non-gelling stable zein solutions in aqueous alcohol by this process is essential for the present invention.

Assuming the Emil Fischer's conception that proteins are built up from amino acids and represent high-molecular polypeptides with the principal peptide (CONH--) linkage, no differences in the structure of globular proteins and fibrous proteins could be expected.

Already in 1928 in the Konstitution und K0n-' figuration der Eiweissstofle, page 35, and in 1933 in the "Des Protein," page 19, I showed that in the structural unit of the native protein in vivo instead of a peptide linkage a "peptidebetain linkage has to be assumed resulting from two proteyls, belonging to two diiferent structural elementary units which are in space configurated and are built up from six proteyls in cis and transform --N=. =oon---- an +1112 on" forming the elementary unit with six proteyls as follows:

Ratio azbzc:

symbolized as o.

Eight such elementary units, connected by peptide-betain linkages.

0 530 consisting of 8 6=48 proteyls. would form a micelle, symbolized as O.

A protein of first degree would consist of 6 micelles with 6.(8x6)=288 proteyls, symbolized Two such proteyls would result by polymerization of two mol alpha amino acids in the "zwitter ion form" as follows:

NHs :IEIHM an as toon- -on NHs '-''NH an an (500- This three-dimensional network of proteyls with the betain-linkage, which, as I assume, is

essential to the proteins of the globular typ would change by the action of phthalic anhydride or other anhydrides of dibasic acids such as maleic anhydride in a bundle of polypeptide chains resulting from the conversion of the elementary units in coplanar polypeptide chains. finally in such of the beta keratin type. as

Two adjoining elementary units bound to- 'gether with one to three betain-peptide linkage resulting from two adjoining aminoacids 17H: would appear to be bound by an oxygen atom. A parallelism is to be found in the intramolecular alkylated amino acids.

C COUCH: o on, T on,

:)z N(CH:):

The following illustrative examples will serve to show specific details of the invention, however, it is to be understood that the specific dearrangement of the betaines into esters of tails, the solutions of the present invention in combination with plasticizers, such as dibutyltartrate, butylstearate, triethanolamine, phenol. cardanol, toluenesulphonylethyiamide, phthalates of mon'oalkylethers of glycol, thiozonides prepared from 2 mol isophorone, 3 mol sulfur, 2 mol triethanolamine and 1 mol fatty alkylamine. or fatty acidamides as described in my copending application Ser. No. 521,978, filed February 11, 1944, and oxazolines prepared from isophorone, unsaturated fatty acids and 1.2 hydroxy alkyl amines as described in my copending application Ser. No. 474,492, filed February 2, 1943, are essential to produce commercial products as coatings on fabrics, paper, wood, metal, rubberlike materials and plastics, corn meal fibers and films.

Example 1 19 g. ammonium thiocyanide, 23 g. monochloracetic acid, 39 g. phthalic anhydride and 500 g. zein are dissolved in 1000 g. per cent denatured alcohol under stirring. The mixture is then heated for 15 minutes under reflux in a water bath of to C. and afterwards cooled. One obtains thus an aqueous alcoholic solution of 5 phthaliden-3 zein pseudothiohydantoin.

Example 2 The procedure is the same as described in Example l. Afterwards the solution is mixed with 200 g. trlethanolamine-mono-n.decylamine-isophorone-thiozonide and 200 g. formalin 40 per cent.

Example 3 The procedure is the same as in Example 1 only with the difference that 13 g. ammoniumthiocyanide, 17 g. monochloracetic acid, 25 g. phthalic anhydride and 350 zein are dissolved in 1000 g. 90 per cent den. alcohol.

Example 4 7.6 g. ammoniumthiocyanide, 10 g. monochloracetic acid, 15 g. phthalic anhydride or 9.8 g. maleic anhydride and 200 g. zein are dissolved in 1000 g. 90 per cent den. alcohol under stirring. The mixture is then heated for 15 minutes under reflux in a water bath of 95 to 100 C. and afterwards cooled. The thus obtained spinning solution is mixed with 40 g. oxazoline, prepared from 1 mol isophorone, 1 mol maleic anhvdride and 2 mol monoethanolamine.

Example 5 The procedure ample 4. Fibers are prepared by extrusion of this solution after addition of 50 g. hydrogen peroxide 3% into a coagulating bath containing formaldehyde and sodium chloride.

Example 6 Example 7 The procedure is the same as described in Example 1. Afterwards the solution is mixed with 100g. thiozonide, prepared from -2 mol isophorone,

is the same as described in Ex- 3 mol sulfur, 3 mol triethanolamine and 50 g. walnut shell flour. The mixture is then poured into molds with additional 200 g. formalin 40 per cent.

By solvent evaporation and curing by reaction with the aldehyde and air oxidation 9. rubberlike material is obtained.

Example 8 7.6 ammoniumthiocyanide, 10 g. monochloracetic acid, g. phthalic anhydride or 9.8 g. maleic anhydride and 200 g. gelatine (glue) are dissolved in 1000 g. water by heating for minutes in a boiling water,,bath. The thus obtained solution is'mixed with 40 g. thiozonide, prepared from 2 mol isophorone, 3 mol sulfur. 2 mol triethanolamine and 1 mol octadecenylamine.

Example 9 3.8 g. ammoniumthiozonide, 4.8 g. monochior acetic acid, '7 g. phthalic anhydride or 4.9 g. maleic anhydride and 200 g. zein are dissolved in 200 g. triethylenglycol and 140 g. triethanolamine by heating for a half hour in a water bath of to C. under stirring. The solution is then cooled to 50 C. and mixed with g. suli'onated castor oil. The composition may be used in the manufacture of soya bean flbers as additional product to the spinning solution or for preparing an aqueous emulsion by pouring 100 parts (by weight) of the composition in 900 parts of water, containing 6 parts of formalin so per cent. Such an emulsion is advantageously used for'after-treatment of soya fibers and casein fibers or for a permanent, shrink and oreaseproof finish by impregnating fabrics and curing them at a temperature of 350 F. for 3 to 4 minutes and washing, drying, framing the cured fabrics.

Having now particularly described and ascertained the nature of my invention and in what manner the same is to be performed, I declare what I claim is:

1. A process of producing condensation products, which comprises, reacting pseudothiohydantnin-3 zein with dibasic acid anhydrides.

2. A process of producing'condensation products, which comprises, reacting pseudothiohydantoin-3 zein with phthalic anhydride.

3. The new compound, 5 phthaliden-pseudothiohydantoin-3 zein, useful to prepare films, filaments, plastics and coatings, having the forwherein zein stands for the zein radical, zein signified as zein'-NH:.

4. New compounds, condensation products of pseudothiohydantoin-3 zein with dibasic acid anhydrides.

. OSKAR HUPPERT. 

